Iron additives are effective in the anaerobic sewage sludge digestion process, but the composition and dosage of these additives are not precisely defined. This research investigates the effects of three iron oxides-based additives on the destruction of volatile solids, the production and quality of biogas, as well as the quality of the supernatant. Additive No 1 contained >41.5% of FeO and >41.5% of Fe2O3, additive No 2 contained ≥86% of Fe3O4, and additive No 3 contained ≥98% of Fe3O4. The best results were obtained by applying an iron oxides-based additive with a higher content of divalent iron oxide. The increase in efficiency of the VSs destruction was not significant and on average 2.2%. The increase in biogas production was on average 20% while the average increase in the content of methane in the biogas was 6.3%. Applying the additive, the reduction in the concentration of ammonium nitrogen in the supernatant was up to 28%, as well as a reduction in the concentration of phosphate phosphorus in the supernatant by up to 3.1 times could be expected compared to the case when the additive was not applied. The dose of additive No 1 was between 7.5 g/kg of dry solids and 15 g/kg of dry solids in the lab-scale test. The dose was specified in the full-scale test, and the recommended dose of the additive was 10 g/kg of dry solids to improve biogas production.